| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1345604 | Tetrahedron: Asymmetry | 2016 | 13 Pages |
A facile and practical approach was developed for the synthesis of chiral α-, β- and δ-aminoalcohols and S-containing heterocyclic analogues by using of readily available sources of chirality. The synthetic strategy involves utilization of camphor-derived ferrocene-containing starting compounds allowing, by means of nucleophilic additions of functionalized organolithiums, for the preparation of a small library of structurally diverse multifunctional derivatives possessing the bicyclic camphane skeleton as the central core. The new diastereoisomeric pure aminoalcohols and S-containing heterocyclic analogues have been evaluated as precatalysts for the addition of diethyl zinc to benzaldehyde providing in some cases very high enantioselectivity (up to 96%).
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(1R,2R,4S,E)-3-(Ferrocenylmethylidene)-2-(2-(dimethylamino)phenyl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-olC29H35FeNO[α]D20 = −136.9 (c 0.41, CHCl3)Source of chirality: (1R)-(+)-camphorAbsolute configuration: (1R,2R,4S,E)
(1R,2R,4S,E)-3-(Ferrocenylmethylidene)-2-(2-((dimethylamino)methyl)-3-(trimethylsilyl)phenyl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-olC33H45FeNOSi[α]D20 = −381.8 (c 0.40, CHCl3)Source of chirality: (1R)-(+)-camphorAbsolute configuration: (1R,2R,4S,E)
(1R,2R,4S,E)-3-(Ferrocenylmethylidene)-2-(2-((dimethylamino)methyl)phenyl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-olC30H37FeNO[α]D20 = −389.7 (c 1.00, CHCl3)Source of chirality: (1R)-(+)-camphorAbsolute configuration: (1R,2R,4S,E)
(1R,2R,4S,E)-3-(Ferrocenylmethylidene)-2-(3-(dimethylamino)propyl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-olC26H37FeNO[α]D20 = −31.0 (c 0.58, CHCl3)Source of chirality: (1R)-(+)-camphorAbsolute configuration: (1R,2R,4S,E)
(1R,2R,4S,E)-3-(Ferrocenylmethylidene)-1,7,7-trimethyl-2-(thiophen-2-yl)bicyclo[2.2.1]heptan-2-olC25H28FeOS[α]D20 = −261.0 (c 1.29, hexane)Source of chirality: (1R)-(+)-camphorAbsolute configuration: (1R,2R,4S,E)
1-((1S,2R,4S,E)-3-(Ferrocenylmethylidene)-2-(3-(dimethylamino)propyl)-2-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-1-yl)-N,N-dimethylmethanesulfonamideC28H42FeN2O3S[α]D20 = −68.3 (c 0.38, CHCl3)Source of chirality: (1S)-(+)-camphor-10-sulfonyl chlorideAbsolute configuration: (1S,2R,4S,E)
1-((1S,2R,4S,E)-3-Ferrocenylmethylidene-2-hydroxy-2-(1-isopropyl-1H-imidazol-2-yl)-7,7-dimethylbicyclo[2.2.1]heptan-1-yl)-N,N-dimethylmethanesulfonamideC29H39FeN3O3S[α]D20 = −339.0 (c 0.64, CHCl3)Source of chirality: (1S)-(+)-camphor-10-sulfonyl chlorideAbsolute configuration: (1S,2R,4S,E)
1-((1S,2R,4S,E)-2-(Benzo[b]thiophen-2-yl)-3-ferrocenylmethylidene-2-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-1-yl)-N,N-dimethylmethanesulfonamideC31H35FeNO3S2[α]D20 = −256.3 (c 1.00, CHCl3)Source of chirality: (1S)-(+)-camphor-10-sulfonyl chlorideAbsolute configuration: (1S,2R,4S,E)
1-((1S,2R,4S,E)-3-Ferrocenylmethylidene-2-(dibenzo[b,d]thiophen-4-yl)-2-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-1-yl)-N,N-dimethylmethanesulfonamideC35H37FeNO3S2[α]D20 = −216.2 (c 0.63, CHCl3)Source of chirality: (1S)-(+)-camphor-10-sulfonyl chlorideAbsolute configuration: (1S,2R,4S,E)
1-((1S,2R,4S,E)-3-Ferrocenylmethylidene-2-hydroxy-7,7-dimethyl-2-(5-(trimethylsilyl)thiophen-2-yl)bicyclo[2.2.1]heptan-1-yl)-N,N-dimethylmethanesulfonamideC30H41FeNO3S2Si[α]D20 = −210.2 (c 1.00, CHCl3)Source of chirality: (1S)-(+)-camphor-10-sulfonyl chlorideAbsolute configuration: (1S,2R,4S,E)
1-((1S,2R,4S,E)-2-(Benzo[d]thiazol-2-yl)-3-ferrocenylmethylidene-2-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-1-yl)-N,N-dimethylmethanesulfonamideC30H34FeN2O3S2[α]D20 = −208.9 (c 0.34, CHCl3)Source of chirality: (1S)-(+)-camphor-10-sulfonyl chlorideAbsolute configuration: (1S,2R,4S,E)
2-((1R,2R,4S,E)-3-Ferrocenylmethylidene-2-hydroxy-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl)acetonitrileC23H27FeNO[α]D20 = −49.0 (c 0.74, CHCl3)Source of chirality: (1R)-(+)-camphorAbsolute configuration: (1R,2R,4S,E)
1-((1S,2R,4S,E)-2-(Cyanomethyl)-3-ferrocenylmethylidene-2-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-1-yl)-N,N-dimethylmethanesulfonamideC25H32FeN2O3S[α]D20 = −98.7 (c 0.54, CHCl3)Source of chirality: (1S)-(+)-camphor-10-sulfonyl chlorideAbsolute configuration: (1S,2R,4S,E)
(1R,2R,4S,E)-2-(2-Aminoethyl)-3-ferrocenylmethylidene-1,7,7-trimethylbicyclo[2.2.1]heptan-2-olC23H31FeNO[α]D20 = −20.5 (c 0.44, CHCl3)Source of chirality: (1R)-(+)-camphorAbsolute configuration: (1R,2R,4S,E)
1-((1S,2R,4S,E)-2-(2-Aminoethyl)-3-ferrocenylmethylidene-2-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-1-yl)-N,N-dimethylmethanesulfonamideC25H36FeN2O3S[α]D20 = −28.2 (c 0.54, CHCl3)Source of chirality: (1S)-(+)-camphor-10-sulfonyl chlorideAbsolute configuration: (1S,2R,4S,E)
(1R,2R,4S,E)-3-Ferrocenylmethylidene-2-(2-(isoindolin-2-yl)ethyl)-1,7,7-trimethylbicyclo[2.2.1]C31H37FeNO[α]D20 = +51.3 (c 0.39, CHCl3)Source of chirality: (1R)-(+)-camphorAbsolute configuration: (1R,2R,4S,E)
1-((1S,2R,4S,E)-3-Ferrocenylmethylidene-2-hydroxy-2-(2-(isoindolin-2-yl)ethyl)-7,7-dimethylbicyclo[2.2.1]heptan-1-yl)-N,N-dimethylmethanesulfonamideC33H42FeN2O3S[α]D20 = +16.7 (c 0.18, CHCl3)Source of chirality: (1S)-(+)-camphor-10-sulfonyl chlorideAbsolute configuration: (1S,2R,4S,E)
